Production of peroxy compounds

ABSTRACT

IN THE PRODUCTION OF 1,1&#39;&#39;-PEROXYDICYCLOHEXYLAMINE FROM DIHYDROXYDICYCLOHEXYL PEROXIDE, OR SUBSTANCES GIVING DIHYDROXYDICYCLOHEXYL PEROXIDE UNDER THE REACTION CONDITIONS, WITH AMMONIA, IMPROVED RESULTS ARE OBTAINED BY CARRYING OUT THE REACTION IN THE PRESENCE OF AMMONIUM CHLORIDE.

United States Patent Oce 3,576,817 Patented Apr. 27, 1971 3,576,817PRODUCTION OF PEROXY COMPOUNPS Brian Walton Harris, Horley, Surrey,England, assignor to BP Chemicals (U.K.) Limited, London, England NoDrawing. Filed May 8, 1968, Ser. No. 727,716 Claims priority,application Great Britain, May 25, 1967, 24,271/ 67 Int. Cl. C07d 85/26US. Cl. 260307 14 Claims ABSTRACT OF THE DISCLOSURE In the production ofl,1peroxydicyclohexylamine from dihydroxydicyclohexyl peroxide, orsubstances giving dihydroxydicyclohexyl peroxide under the reactionconditions, with ammonia, improved results are obtained by carrying outthe reaction in the presence of ammonium chloride.

The present invention relates to a process for the production of1,1'-peroxydicyclohexylamine.

1,l'-peroxydicyclohexylamine, herein after referred to as peroxyamine(I) and processes for its production and use an intermediate forproducing resinous monomers are described in Belgian Patent 701,327.This patent describes a process for making peroxyamine (I) by reactionof 1,1- dihydroxydicyclohexyl peroxide, hereinafter referred to asperoxide (II), or substances giving peroxide (II) under the reactionconditions, with ammonia. Thus peroxyamine (I) may be prepared byreaction of hydrogen peroxide, cyclohexanone and ammonia.

According to the present invention a process for producingl,1-peroxydicyclohexylamine comprises reacting 1,1-dihydroxydicyclohexyl peroxide, or substances giving 1,1-dihydroxydicyclohexyl peroxide under the reaction conditions, withammonia in the presence of ammonium chloride.

Peroxide (II) and processes for its preparation are described in theliterature, for example J.A.C.S., vol. 61, p. 2430, paper by N. A. Milasand co-workers. Examples of substances capable of giving rise toperoxide (II) under the reaction conditions are mixtures of hydrogenperoxide and cyclohexanone. Examples of suitable forms in which thehydrogen peroxide may be fed to the reaction are'aqueous solutions,which may vary in strength over a wide range and examples of suiatbleconcentrations are those in the range -40% by weight of hydrogenperoxide, for example solutions containing about of hydrogen peroxide byweight. However, hydrogen peroxide solutions containing as little as 2%by weight of hydrogen peroxide may be used.

When using mixtures of hydrogen peroxide and cyclohexanone, hydrogenperoxide stabilizers for example sodium ethylene diamine tetra-acetate(E.D.T.A.) may be added to the reaction mixture.

Ammonia which is reacted with peroxide (II) or substances givingperoxide (II) under the reaction conditions may be fed to the reactionin the gaseous or in the liquid phase, e.g. in the form of an aqueoussolution. When ammonia solutions are used, the concentration is not verycritical and an example of a solution which may be used is thecommercially available solution having a relative density of 0.880. Itis preferable to use an excess which need only be a slight excess ofammonia, over the stoichiometric quantity, i.e. a molar ratio of ammoniato peroxide (II) slightly greater than 1:1. Where substances givingperoxide (II) under the reaction conditions are used, the stoichiometricquantity of ammonia is the number of moles of ammonia which equals thenumber of moles of peroxide (II), which could notionally be formed. Thus2 moles of cyclohexanone and 1 mole of hydrogen peroxide can give 1 moleof peroxide (H) and with these quantities of cyclohexanone and hydrogenperoxide the stoichiometric quantity of ammonia is 1 mole.

When the hydrogen peroxide, cyclohexanone and ammonia are used, themolar ratios in which they are brought into contact may be thestoichiometric one, i.e. 1:221 or may vary widely from thestoichiometric ratio. Thus the conversion of cyclohexanone may beincreased by using an excess of hydrogen peroxide but this is oftenundesirable as the excess hydrogen peroxide tends to be decomposed andlost. Excess cyclohexanone and ammonia, however can be recovered and asindicated above the use of at least a slight excess of ammonia ispreferred. The use of excess cyclohexanone is also often beneficial.Examples of molar ratios of cyclohexanone to hydrogen peroxide which maybe used are 5:1 to 1.311.

The peroxide (II) or substances giving peroxide (11) under the reactionconditions may be reacted with the ammonia by mixing the reactantstogether, optionally in a solvent for peroxide (II) or the substancesgiving peroxide (II) under the reaction conditions, e.g. lower alkanols,such as ethanol or methanol. Where the reaction mixture containsappreciable amounts of water as a result of the use of aqueous hydrogenperoxide and/or aqueous ammonia, a substance which is a solvent for theperoxide (II), or for non-water soluble substances giving peroxide (II)under the reaction conditions (e.g. the cyclohexanone constituent of thecyclohexanone/ hydrogen peroxide mixture), and which is miscible with,or highly soluble in, water may be used. However it is not necessary tocarry out the reaction with peroxide (II) in solution, and satisfactoryresults may be obtained by reacting ammonia with a suspension ofperoxide (H). Similarly it is not necessary to use a water-misciblesolvent for cyclohexanone where cyclohexanone is a reactant. It ispreferred to avoid the presence of very large quantities of water in thereaction mixture but the presence of some water may be desirable.

The concentration of the ammonium chloride in the reaction mixture mayvary over a moderately wide range, for example from 2 to 20% by weight,in particular 2 to 10% by weight.

The reaction of peroxide (II), or substances giving peroxide (II) underreaction conditions, with ammonia may be carried out over a moderatelywide range of temperatures. The use of high temperatures is preferablyavoided as this may lead to some decomposition of peroxy compounds,while at very low temperatures the reaction is inconveniently slow. Anexample of a suitable range of temperatures is the range 0 to 50 C. andin particular temperatures in the range 20 to 40 C. a

The reaction time will depend on the temperatures used, being longer atlower temperatures. At temperatures of 30 to 50 C. quite high yields areobtained after about 2 hours.

Efiicient mixing of the reactants is advantageous. The

method. The best method of recovering peroxyamine (I) may depend on theway in which the reaction is carried out. If the reaction is carried outusing aqueous ammonia, hydrogen peroxide, and cyclohexanone attemperatures below about 20, then initially 1,1-dihydroxydicyclohexylperoxide (II) separates out as a solid, but towards the end of thereaction period an oil layer forms at the bottom of the reaction vessel.This layer contains the peroxyamine (I) together with some unreactedcyclohexanone. This crude peroxyamine may be separated as an oil,filtered off as a solid precipitate after chilling to 10 C. or extractedinto a suitable water-immiscible organic solvent e.g. ether, chloroform,light petroleum or benzene which is subsequently removed bydistillation.

The crude peroxyamine may be purified by any convenient means, forexample the lower boiling impurities may be removed by distillation andthe peroxyamine then 3 distilled under sub-atmospheric pressure or thecrude peroxyamine may be dissolved in a suitable solvent, concentratedand crystallised preferably at about C. When the crude peroxyamine isextracted from the reaction mixture into a solvent this solution may beconcentrated and 4 050 C., 1,1'-dihydroxydicyclohexyl peroxide, orcyclohexanone and hydrogen peroxide with ammonia in the presence ofammonium chloride.

2. A process according to claim 1 wherein the hydrogen peroxide is fedto the reaction in the form of an chilled to give pure peroxyaminecrystals. Alternatively aqueous solution. the crude peroxyamine may bedissolved in awater misci- 3. The process according to claim 2 whereinthe conble solvent, e.g. ethanol and the resulting solution may becentration of hydrogen peroxide in the aqueous solution run into a largevolume of water causing the peroxide (I) is in the range 20 to 40% byweight. to be precipitated as a solid which can be filtered off. 4. Theprocess according to claim 1 wherein the con- For some uses the crudeperoxyamine oil may be used centration of the ammonium chloride in thereaction mixas such; alternatively it may only be necessary to dry theture is in the range 1 to by weight. crude peroxyamine oil by contactwith a drying agent or 5. The process according to claim 4 wherein theconby removing the water by vacuum distillation. If the centration ofammonium chloride is in the range 2 to ammonia gas is passed into amixture of cyclohexanone, 15 10% by weight. ammonium chloride andhydrogen peroxide which may 6. The process according to claim 1 whereinammonia also contain a cyclohexanone solubilizer, e.g. methanol, is fedto the reaction as an aqueous solution. and a hydrogen peroxidestabilizer, e.g. sodium E.D.T.A., 7. The process according to claim 1wherein ammonia at a temperature above room temperature, e.g. to 40 isfed to the reaction as a gas. C., for several hours and the resultingmixture is allowed 20 8. The process according to claim 1 where aquantity to stand and cool for e.g. 10 to 15 hours, then a precipiofammonia in excess of the stoichiometric quantity is tate of crystallineperoxide (I) may be obtained which brought into contact with1,1'-dihydroxydicyclohexyl permay be filtered oil without furtherseparation. The yield oxide or cyclohexanone and hydrogen peroxide. ofperoxide (I) from this method using additional gase- 9. The processaccording to claim 1 wherein cyclohexous ammonia was higher than thatobtained using aque- 5 anone and hydrogen peroxide are brought intocontact ous ammonia alone. with ammonia in a molar ratio ofcyclohexanone to hy- The invention will now be illustrated by referenceto drogen peroxide in the range 5:1 to 1.3:1. the following examples inwhich all temperatures are in 10. The process according to claim 4wherein the 1,1- degrees Celsius. dihydroxydicyclohexyl peroxide orsubstances giving 1,1- EXAMPLES 3o dihydroxydicyclohexyl peroxide underthe reaction con- A series of tests was carried out in whichcyclohexadifions i reacted with ammonia by mixing the t i none, 0.880ammonia solution (an aqueous solution of togethei. m the presence. asolvent for the ammonia having a density of 0.880 gram per millilitre),dmxydlcyclohgyl peroxlde for the cyclohexanone and the sodium salt ofethylene diamine tetra-acetic acid, hydrogen peroxlde' methanol (whenused), and accelerator or catalyst (when i Process accordmg to claim 10'wherem the used) were vigorously stirred together and an aqueoussolvent 15 a lower alkanol' solution containing 28% by weight hydrogenperoxide The prqcess accordmg to Clalm 11 Wherem the added gradually,keeping the temperature below 10. 1,1'- lowel alkanol 18 ethanolmathan9l' dihydroxydicyclohexyl peroxide separated out as a solid TheProcess according clam 4 :Wherem the over 5-30 minutes. The temperaturewas raised to 40 d1hydrXyd1cyc1Phey1 peroxlqe or cyclohefxanone f andammonia gas Passed into the solution After two hydrogen peroxlde isbrought into contact with ammonia hours the yield f peroxyamine (I) wasdetermined by and ammonium chloride at temperatures in the range 0extraction of the crude product with petroleum ether-folto lowed by theremoval of the ether and analysis of the The Process according to claim13 wherein the crystals obtained. 45 temperature is in the range 20 to40 C.

TABLE 1 Reaetants, solvents etc.

Yield of 1,1'-peroxydicyelohexyl- 28% by wt. 0.880 Sodium salt amine asa per- Cyclo hydrogen ammonia of ethylene centage of theorehexanoneperoxide solution Methanol diamine tetra tical yield based Run No (g.)(ml (ml) (m1.) acetic acid (g.) Accelerator on cyelohexanone 1 450 279350 225 5 None 73.1 2 450 279 350 None 5 None 75.4 3 450 279 350 Non 5Ammonium chloride, 48.5 g. 81. 3 4 450 279 350 None 5 Sodiumnltrate,48.5 g.-- 75.8 450 279 350 225 5 Sodium chloride, 48.5 g 76. 5270 156 210 135 3 Sodium sulphate, 29.0 g- 74.5 360 223 280 180 4Ammonium sulphate, 38.7 g 63.0 450 279 350 225 5 Ammonium carbonate,48.5 g 60. 0 the'fshelguggltitieos so: the rflaftgntsdand soliletrlltsused and References Cited 1e per x mine ase on cyc o exanone arerecorded in the accompanying table. This table shows that UNITED STATESPATENTS ammonium salts or chloride salts per se do not give any3,252,979 5/1966 Oswald 260"'563X marked improvement and may evendepress the yield of OTHER REFERENCES peroxyamine (I). High yields areobtained only with the specific compound ammonium chloride.

I claim:

1. The process for producing l,1'-peroxydicyclohexyl- Derwent: BelgianPatent Report No. 12/68, Abstract of Belgian Patent 704,214 of Mar. 22,1968.

ALEX MAZEL, Primary Examiner amine which comprises reacting at atemperature of from RUSH, Assistant l'

